Gelatin coating compositions containing a mixture of sodium maleopimarate and a sucrose ester of an aliphatic acid

ABSTRACT

COATING PROCESS AND COMPOSITIONS OF MATTER COATED THEREBY COMPRISING GELATIN AND CONTAINING THEREIN, AS A COATING AID, A MIXTURE OF SODIUM MALEOPIMARATE AND A SUCROSE ESTER OF AN ALIPHATIC ACID ARE DISCLOSED. SAID PROCESSES AND COATING COMPOSITIONS FIND PARTICULARLY GOOD USAGE IN PHOTOGRAPHIC LAYERS, EMULSIONS AND ELEMENTS.

GELATIN COATING COMPOSITIONS CONTAIN- ING A MIXTURE OF SODIUMMALEOPIMARATE AND A SUCROSE ESTER OF AN ALIPHATIC ACID William J. Knox,Jr., Rochester, N.Y., assignor to Eastman Kodak Company, Rochester,N.Y., a corporation of New Jersey No Drawing. Continuation-impart ofapplication Ser. No. 365,180, May 5, 1964. This application Sept. 11,1964, Ser. No. 395,949

Int. Cl. G03c ]/38 US. Cl. 96-1145 11 Claims ABSTRACT OF THE DISCLOSURECoating processes and compositions of matter coated thereby comprisinggelatin and containing therein, as a coating aid, a mixture of sodiummaleopimarate and a sucrose ester of an aliphatic acid are disclosed.Said processes and coating compositions find particularly good usage inphotographic layers, emulsions and elements.

This application is a continuation-in-part of application Ser. No.365,180, filed May 5, 1964.

This invention relates to gelatin coating compositions particularly foruse in the manufacture of photographic products, involving the use ofsucrose esters of fatty acids of 8-18 carbon atoms (or their mixtureswith sodium maleopimarate) as coating aids therein.

In the application of gelatin layers to a surface particularly in themaking of photographic products, it is usually desirable to include inthe composition a coating aid to facilitate the aplication of thecomposition Onto a surface. Saponin has been widely used for thispurpose but being a natural material it varies in uniformity andeffectiveness and is subject to contamination when obtaining it from itssource.

Various coating aids have been mentioned in the prior art, many of whichare unusually effective for some particular use. However, thesurfactants heretofore suggested as coating aids often leave somethingto be desired, hence, those which have been suggested heretofore cannotbe considered as of universal application in the laying down of gelatinlayers.

Sodium maleopimarate has been suggested as a coating aid in Knox andFowler US. Pat. No. 2,823,123. However, this material when used alonedoes not impart to the final product a rewettability sufficient for mostmechanical processing. This deficiency has heretofore been overcome byusing saponin therewith. This does not achieve the goal of completeelimination of saponin from coating operations.

One object of my invention is to provide gelatin coating compositionsadapted for use in photographic products. Another object of my inventionis to provide gelatin coating compositions containing certain sucroseesters of fatty acids as coating aids. A further object of my inventionis to provide a coating aid for gelatin which makes United States Patentpossible the simultaneous application onto a support of gelatin-silverhalide photographic emulsion layers and gelatin overcoatings without anysubstantial amount of defects in the products obtained. A still furtherobject of my invention is to provide gelatin layers, containing coatingaid, characterized by excellent rewettability without excessivereduction of surface friction. Other objects of my invention will appearherein.

My invention is directed to gelatin coating compositions either aqueoussolutions of gelatin or photographic emulsions, the latter ordinarilybeing composed of an aqueous solution of gelatin containing as the lightsensitive material a silver halide, which compositions contain as acoating aid therein a sucrose ester of a fatty acid of 8-18 carbon atomswith or without the addition of sodium maleopimarate. The compositionsmay contain other added materials such as dyes, hardeners, antifoggants,stabilizers, plasticizers, pigments or the like.

The coating aid is employed in a proportion which is effective inimparting good coating properties to the gelatin composition. Ordinarilya proportion of coating aid of from 0.1% to 10% based on the dry weightof the gelatin composition is effective, however, the coating aid inaccordance with my invention improves the coating properties of thegelatin composition when present in almost any proportion. When sodiummaleopimarate is used in conjunction with the sucrose ester as thecoating aid, the proportion of the two materials may vary greatly fromas much as nine parts of sodium maleopimarate to one part of sucroseester through equal parts to a predominating proportion in the coatingaid of the sucrose ester.

The sucrose esters which are useful as coating aids in gelatincompositions are the sucrose esters of fatty acids, =both saturated andunsaturated, having 8 or more, but more particularly 12-18, carbonatoms. For example, the monolaurate, the monomyristate, the monooleate,etc. of sucrose have shown usefulness in gelatin compositions inaccordance with my invention.

Coating aids in accordance with the invention have shown themselves tobe especially useful in gelatin compositions to be employed inmultilayer coating techniques as described in US. Pat. No. 2,761,791 ofRussell. This coating method is especially useful in the manufacture ofphotographic film and photographic paper by application to a support ofone or more light sensitive e'mulsions and/or subcoatings, protectivecoatings, light filtering layers, overcoatings and the like appliedsimultaneously whereby a distinct layer relationship and desiredthickness of each layer is obtained. These compositions are useful inthe making of products in either black and white or color photography orfor similar situations in which gelatin coatings are applied to asupport such as paper, film base such as of the' cellulose ester orpolyethylene terephthalate type or to some other supporting material.

In one example of the invention a silver halide photographic emulsionusing gelatin as the vehicle was prepared and sucrose monolaurate wasadded as the coating aid. Also prepared were plain gelatin compositionsand layers of both, the emulsion and the gelatin composition (as anovercoating over the emulsion) were applied simultaneously. Theconcentrations of the sucrose monolaurate in the emulsion and in theovercoating were varied in accordance with the proportions given in theaccompanying table. The coating was applied in the manner described inRussell US. Pat. No. 2,761,791, the coating having been carried out at aspeed of 60 ft. per minute and at a temperature of 95 F. It appearedthat the presence of the sucrose monolaurate aided in the coatingoperation and better repellency values were obtained than where thatmaterial was not present. The coatings were made at the proportionsspecified and the repellency occurrences for the most part remainedfairly low particularly where the proportions of coating aid in bothlayers were somewhat commensurate. The products obtained in thisoperation sometimes had a low coefficient of friction which in somecases tended to cause difficulty in handling. In other runs sodiummaleopimarate was also present as part of the coating aid and theslipperiness was reduced when that feature was considered to be of someimportance.

TABLE II Surfactant concentration, wet Repellenemulsion cies,

Blank Q gt (control)- Gelatin-silver halide photographic emulsions weresupplied with sucrose monomyristate as a coating aid and those emulsionsand gelatin overcoating layers containing sucrose monomyristate wereapplied in a hopper coating TABLE 1 procedure to paper by the methoddescribed in the Russell i ggf ggg 5 patent referred to. The coating wasapplied to the support at the rate of 60 ft. per minute, the temperaturebeing l g Repellencies 05 F. The proportions of surfactant and dataconcern- (g./lb.) (g./1b.) 7.5 it! mg the products are shown 111 theabove table.

0 13 (113 0 In some cases it has been thought desirable to add 0 0.15 0sodium maleopimarate as a portion of the coating aid. 8: Myriag Forexample, a silver halide gelatin emulsion and a clear 0.13 0.25 1gelatin overcoat were applied by a multilayer technique 13g 83g? topaper by the method described in the Russell patent 1. 0 0.25 Myriadreferred to above. The runs resulting were divided into 81 3;; gexamples using various proportions for the coating aid. 1.5 0.2 0 Theproportions of the maleopimarate (SMP) to 0. 3 1 5 sucrose monomyristate(SMM) the concentrations of sur- 0- 5 1 -0 0 factant used in theemulsion and in the overcoat and the 1 :8 3 results obtained bymeasuring various physical properties were as follows:

Surfactant concentration Developer Repel- In emulsion, In 800, spreadCoetlicient lencies SMPzSMM ratio g./lb. ./1b. (0111. of friction (7.5It!) 0. 0 0. 5 5. 31 0. 53 None 1 0.13 0.5 5.72 0.54 Nono 0. 25 0. 5 0.e2 0. 52 I 0. 0. 5 1e. 0. 45 None 0. 0 0. 5 5. 72 0. 47 None 4 0. 13 0.5 13. 20 0. 46 None 0. 25 0. 5 16. 60 0. 42 None 0.50 0.5 16 60 0.43None 0. 0 0. 5 5. 31 0. 45 N one T3 0. 13 O. 6 13. 90 0. 37 None 0.25 0.5 16 00 0 37 None 0.50 o. 5 16.60 0 40 None 0. 0 0. 5 16.00 0 30 None M0.13 0.5 16. 60 0 33 None 0. 25 0. 5 10. 60 0 20 None 0. 50 0. 5 10. 000 32 None 1 Simultaneous overcoat.

2 Small.

As a further example of coating with a gelatin composition in whichsucrose monolaurate has been incorporated as a coating aid, thatmaterial was incorporated into photographic emulsion in the proportionsindicated. The concentration of the sucrose monolaurate in the wetemulsion and the repellencies of the coated products ob- 7 madeinvolving the simultaneous application to paper ing as a coating aidtherein a mixture of sodium maleopimarate and sucrose monococoate.

5. A composition of matter comprising gelatin containing as a coatingaid therein a mixture of sodium maleopimarate and sucrose monolaurate.

6. A gelatin-silver halide photographic emulsion containing as a coatingaid therein a mixture of sodium maleopimarate and a sucrose aliphaticacid ester.

7. The composition of matter according to claim 1 in which theproportions of said sodium maleopimarate SMP AND SUCROSE MONOCOCOAIE ASTHE COATING AID Surfactant concentration Developer Repel- In emulsion,In SOC., spread Coefficient lencies SMP/ester ratio g./1b. g./1b. (cmfl)of friction (7.5 it.)

0. 0 0. 5 4. 90 0. 48 None 9 1 0.13 0. 5 4.15 0.44 None 0. 25 0.5 7.070.51 None 0. 50 0. 5 10. 0. 47 None 0. 0 0. 5 4. 52 0. 48 None 4 1 0. l30. 5 10. 70 0.45 None 0. 0. 5 13. 90 0. 43 None 0. 50 0. 5 16. 60 0. 43None 0. 0 0. 5 6. 16 0. 47 1 7 3 0. l3 0. 5 15. 2O 0. 42 None 0. 25 0. 516. 60 0. 41 None 0. 50 0.5 16. 60 0. None 0. CI 0.5 6. 16 0.39 None 1 10. 13 O. 5 16. 60 0.36 None 0 25 0. 5 16. 60 0.34 None 0. 0. 5 16. 0.351 0. 0 0. 5 16. 60 0. 31 None 3 7 0.13 0.5 16.60 0. 29 None r 0. 25 0. 516. 6O 0. 28 None SMP AND SUCROSE MONOOLEATE AS THE COATING AIDSurfactant concentration Developer Repel- In emulsion, In 800., spreadCoefliclent lencies S MP/ester ratio g./lb. g./lb. (cm?) of friction(7.5 ft.)

0. 0 0. 5 6. 16 0. 54 2 0. 13 0. 5 6. 16 0. 54 1 0. 25 0.5 5. 31 0.50 00. 50 0. 5 13. 20 0. 51 5 0. 0 O. 5 5. 72 0. 44 1 0. 13 0.5 16. 60 0.42None 0. 25 0. 5 16. 60 0. 49 None 0. 50 0. 5 16. 60 0. 43 None 0. 0 0. 59. 62 0. 38 None 0. 13 0.5 06.60 0.38 None 0. 25 0. 5 16. 60 0. 38 None0. 50 0. 5 16. 60 0. 38 None 0. 0 0. 5 16. 60 0. 30 None 0. l3 0. 5 16.60 0.30 None O. 25 0. 5 16. 60 0. 27 None 0. 50 0. 5 16. 60 0. 29 None0. 0 0. 5 16. 60 0. 28 None 0. 13 0.5 16. 60 0. 25

' 0. 25 0. 5 16. 60 0. 26 None 0. 50 0. 5 16. 60 0. 24 None Theinvention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove, and asdefined in the appended claims.

I claim:

1. A composition of matter comprising gelatin containing as a coatingaid therein a mixture of sodium maleopimarate and a sucrose ester of analiphatic acid of 8-18 carbon atoms.

2. A composition of matter comprising gelatin containing as a coatingaid therein a mixture of sodium maleopimarate and sucrose monomyristate.

3. A composition of matter comprising gelatin containing as a coatingaid therein a mixture of sodium maleopimarate and sucrose monooleate.

4. A composition of matter comprising gelatin containand sucrose estermixture are sufficient to impart to said gelatin a developer spread ofnot less than about 5.72

60 cm. and a coeflicient of friction of greater than about 65 and analiphatic monocarboxylic acid ester.

9. In a process of coating a photographic silver halidecontainingelement comprising a support and at least one layer comprising gelatin,the improvement comprising adding to said layer a mixture of sodiummaleopimarate and a sucrose ester of an aliphatic monocarboxylic acid.

10. The process of claim 9 in which said mixture comprises a sucroseester of said acid having more than 8 carbon atoms.

11. The processof claim 9 in which said mixture is comprised ofproportions of sodium maleopimarate and said ester sufiicient to impartto said gelatin, a developer spread of not less than about 5.72 cm. anda coefficient of friction of greater than about 0.29.

References Cited UNITED STATES PATENTS 8 OTHER REFERENCES Hopkins etal., Journal of the American Pharmaceutical Association, vol. 49, pp.220-4 (1960).

Osipow, Journal Society Cosmetic Chemists, vol. 7, pp. 5 249-55 (1956).

Merck Index, Sixth Edition, p. 454, Merck and Company, Rahway, NJ.(1952).

Harris 16791 Knox er a1 96. 94 J. TRAVIS BROWN, Primary Examiner 167 91US. Cl. X.R.

Hagge 61', al. 9694

